WO2016141301A1 - Composites nitrure de bore-liquide ionique et leur utilisation pour des dispositifs de stockage d'énergie - Google Patents

Composites nitrure de bore-liquide ionique et leur utilisation pour des dispositifs de stockage d'énergie Download PDF

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WO2016141301A1
WO2016141301A1 PCT/US2016/020916 US2016020916W WO2016141301A1 WO 2016141301 A1 WO2016141301 A1 WO 2016141301A1 US 2016020916 W US2016020916 W US 2016020916W WO 2016141301 A1 WO2016141301 A1 WO 2016141301A1
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boron nitride
energy storage
electrolyte
storage device
lithium
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PCT/US2016/020916
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English (en)
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Marco T. F. RODRIGUES
Hemtej Gullapalli
Venkata K. KALAGA
Arava L. M. REDDY
Pulickel M. Ajayan
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William Marsh Rice University
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Publication of WO2016141301A1 publication Critical patent/WO2016141301A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/005—Lithium hexafluorophosphate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure pertains to compositions that include a boron nitride, an ionic liquid, and a lithium salt.
  • the ionic liquid in the composition includes a piperidinium-based ionic liquid, such as 1 -methyl- 1 -prop ylpiperidinium bis(trifluoromethylsulfonyl)imide.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
  • the boron nitride in the composition is hexagonal boron nitride.
  • the compositions of the present disclosure are in the form of a composite. In some embodiments, the compositions of the present disclosure are utilized as an electrolyte, a separator, or an electrolyte- separator combination in an energy storage device.
  • the present disclosure pertains to methods of making the compositions of the present disclosure.
  • the methods of the present disclosure include a step of contacting a boron nitride, an ionic liquid, and a lithium salt.
  • the contacting occurs by mixing the boron nitride, the ionic liquid, and the lithium salt.
  • the boron nitride is in solid form while the ionic liquid and the lithium salt are in a solution.
  • the mixing occurs at a 1:2 boron nitride to solution wt./wt. ratio.
  • the methods of the present disclosure also include a step of incorporating the compositions of the present disclosure into an energy storage device.
  • the present disclosure pertains to energy storage devices that contain the compositions of the present disclosure.
  • the compositions of the present disclosure are utilized as electrolytes, separators or electrolyte-separator combinations in the energy storage device.
  • the energy storage device is a battery, such as a lithium-ion battery. In some embodiments, the energy storage device is capable of being operated at temperatures of more than about 100°C.
  • FIGURE 1 provides schemes for making boron nitride-based composite materials (FIGS. 1A-B), and an illustration of a battery that contains the composite materials (FIG. 1C).
  • FIGURE 2 shows the measurement of transport, structural and electrochemical properties of various electrolyte systems, including the boron nitride-based composite materials.
  • FIG. 2A provides an Arrhenius plot of ionic conductivity for the 1 mol L "1 solution of lithium bis(trifluoromethylsulfonyl)imide ("LiTFSI”) in 1 -methyl- 1 -prop ylpiperidinium bis(trifluorosulfonyl)imide (“PP13”), and for the BN- and clay-based composites.
  • FIG. 2B provides the evolution of Tu + with temperature for a hexagonal boron nitride (“h-BN”) composite and for the LiTFSI/PP13 solution.
  • h-BN hexagonal boron nitride
  • FIG. 2C provides the Raman spectra of the BN system in the region of TFSI " full anion vibration.
  • the spectra for LiTFSI solutions in room temperature ionic liquids ("RTILs") with different concentrations is also provided for comparison.
  • the dots are experimental points, and the red line is the fit obtained when combining the two band components.
  • FIG. 2D provides anodic (top) and cathodic (bottom) linear voltammetry scans at 120°C for the neat ionic liquid, the 1 mol L "1 LiTFSI/PP13 solution and the h-BN-based electrolyte. The legends apply for both plots.
  • FIGURE 3 shows the performance of lithium titanate ("LTO") half-cells containing h- BN composites as electrolyte.
  • FIG. 3A provides cyclic voltammograms taken at 120°C with a scan rate of 0.1 mV s "1 , showing symmetric and sharp peaks.
  • FIG. 3B provides cyclic stability for a cell operated for 32 days at a C/8 rate at 120°C, showing stable capacity of 158 mAh g "1 .
  • FIGURE 4 shows perspectives for h-BN composite electrolytes.
  • FIG. 4A provides cyclic voltammetry and
  • FIG. 4B provides cyclic stability of a LTO half-cell containing the h-BN composite tested at 150°C.
  • FIGURE 5 shows compatibility of the h-BN electrolyte with cathode materials.
  • FIG. 5A provides cyclic voltammogram of a Lii +x Mn 2 0 4 (LMO) half-cell tested at 120°C.
  • FIG. 5B provides the charge-discharge profile of the half-cell. The results show that, at high temperatures, the h-BN electrolyte allows performance similar to conventional electrolytes tested at room temperature.
  • FIGURE 6 shows modeling of the ionic conductivities of the electrolytes.
  • FIG. 6A provides a Vogel-Tammann-Fulcher ("VTF") plot for the 1 mol L "1 solution of LiTFSI in PP13.
  • FIG. 6B provides a VTF plot for the h-BN composite.
  • FIG. 6C provides a VTF plot for the clay-based composite.
  • FIGURE 7 shows additional transport properties for the h-BN electrolytes.
  • FIGS. 7A and 7B provide an example of results obtained for determining T L i + for the h-BN composite at 23 °C and 60°C, respectively, showing reduced resistance of the passivation film and an accelerated achievement of the steady state at higher temperatures.
  • FIG. 7C provides typical impedance behavior of symmetric Li/electrolyte/Li cells obtained for the electrolytes (mostly 1 mol L "1 LiTFSI/PP13) at 100°C and 120°C, before and after the potentiostatic polarization employed to measure Tu + . The Nyquist plot was purposely represented with asymmetric axis for clarity.
  • FIGS. 7D-E provide dependence of ionic conductivity and Tu + , respectively, on LiTFSI concentration in PP13 solutions.
  • FIGURE 8 shows scanning electron microscopy ("SEM") images.
  • FIG. 8A provides an SEM image of pure BN.
  • FIG. 8B provides an SEM image of fresh BN-RTIL electrolytes.
  • FIG. 8C provides an SEM image of BN-based electrolyte after 30 cycles in a cathode half-cell. A 10 nm layer of gold was sputtered on top of the samples to minimize charging.
  • FIGURE 9 shows additional electrochemical data for the electrolytes.
  • FIG. 9A provides linear sweep voltammetry showing the electrochemical stability of the electrolytes at room temperature. The anodic scan is on the top, and the cathodic scan is on the bottom.
  • 9B-C provide cyclic voltammograms of the BN electrolyte in a 3-electrode setup (Ni as working electrode and Li metal as both reference and counter) showing a reversible plating/stripping behavior at room temperature and at 120°C, respectively.
  • FIGURE 10 shows additional cyclic stability data at 120°C for LTO half-cells prepared using the h-BN composite (FIGS. lOA-C). The respective C-rate is indicated in the plot.
  • FIG. 10D provides the average coulombic efficiency as a function of the current density for LTO half- cells cycled at 120°C. The values are representative of all cells tested with the same current density.
  • FIG. 10E provides rate capability studies at 120°C.
  • FIG. 10F provides cycling data for the same cells at different temperatures at a C/3 rate.
  • FIGURE 11 shows electrochemical behavior of LTO half-cells operating at 24°C.
  • FIG. 11A provides cyclic voltammograms obtained at a 0.1 mVs scan rate.
  • FIG. 11B provides comparison of charge/discharge profiles between cells cycled at a C/8 rate at room temperature and 120°C. The elevated ionic conductivity and accelerated reaction kinetics at higher temperatures leads to a lower polarization and to large specific capacities.
  • FIG. 11C provides a Nyquist plot from impedance measurements of an uncycled cell.
  • FIG. 11D provides cycling behavior of the cell at a C/8 rate. The scattering in the first few points are due to an initially noisy cycling, sometimes observed at room temperature.
  • FIGURE 12 provides data relating to the characterization of h-BN-based composite electrolytes aged at 120°C before being used in a half-cell.
  • FIG. 12A is a photograph of the electrolyte paste, showing no visible changes even after 20 days of exposure to high temperature. Also shown are Nyquist plots obtained at 120°C for uncycled half-cells assembled using electrolytes aged for 10 days (FIG. 12B) and 20 days (FIG. 12C). The insets, with units in kohm, show the high frequency region.
  • FIG. 12D shows voltammograms for the first five cycles of the half-cell prepared using the h-BN composite aged for 20 days.
  • FIGURE 13 shows electrode aging experiments.
  • FIG. 13A provides delithiation capacities at 25 °C for LTO half-cells assembled using fresh and aged electrodes, with 1 mol L "1 LiPF 6 in EC:DMC 1: 1 (v/v) as electrolyte.
  • FIGS. 13B-D provide electrochemical impedance spectra for cells prepared using a fresh electrode and electrodes aged at 120°C for 10 days and 20 days, respectively. Insets show an amplified view of the high frequency region. All spectra were collected in the delithiated state.
  • FIGURE 14 shows impedance spectra at 120 °C for LTO half-cells containing the h-BN composites at different cycling stages at high temperatures. Shown are fresh cells (FIG. 14A), cells after 5 cycles (FIG. 14B), and cells after 50 cycles (FIG. 14C). A C/8 rate was employed in the experiments. All spectra were collected in the delithiated state.
  • FIGURE 15 shows self-discharge (SD) measurements for a LTO half-cell at 120 °C.
  • FIG. 15A shows charge-discharge profile for the sample allowed to self-discharge for 24 hours.
  • the galvanostatic portion (C/8 rate) is shown as blue, while the SD curve is colored red.
  • FIG. 15B shows the delithiation capacity for each cycle. The 4 th cycle, pointed by the red arrow, is the capacity retrieved after 24 hours of SD.
  • FIGURE 16 shows electrochemical characterization for the LMO-LTO full-cell.
  • FIG. 16A provides cyclic voltammetry for the full-cell using conventional organic electrolytes at room temperature.
  • FIGS. 16B-D provide cyclic voltammetry, charge discharge profile, and cyclic stability, respectively, at 120°C using h-BN composite electrolytes.
  • LIBs lithium- ion batteries
  • LOCs lithium- ion batteries
  • thermal energy storage devices have performance limitations, including limited stability at high temperatures.
  • LIBs lithium- ion batteries
  • high energy density which make them the standard power source for portable devices.
  • LIBs have limited performance even at mildly elevated temperatures, such as temperatures ranging from 60 °C to 80 °C.
  • separators are usually composed of a thin polymeric film, which can soften or shrink upon heating, thereby resulting in electrical short circuit.
  • the present disclosure pertains to compositions that include a boron nitride, an ionic liquid, and a lithium salt.
  • the compositions of the present disclosure can have various types of boron nitrides, ionic liquids and lithium salts at various ratios.
  • the boron nitrides in the compositions of the present disclosure include a boron nitride in a hexagonal phase, such as hexagonal boron nitride.
  • the hexagonal boron nitrides in the compositions of the present disclosure include, without limitation, particulate hexagonal boron nitrides, exfoliated hexagonal boron nitrides (e.g., exfoliated hexagonal boron nitrides where the layers of the structure have been separated into individual flakes), and combinations thereof.
  • compositions of the present disclosure can also have various ionic liquids.
  • the ionic liquids in the compositions of the present disclosure can include, without limitation, imidazolium-based ionic liquids, piperidinium-based ionic liquids, phosphonium-based ionic liquids, ammonium-based ionic liquids and combinations thereof.
  • the ionic liquid is a piperidinium-based ionic liquid, such as 1- methyl- 1-propylpiperidinium bis(trifluoromethylsulfonyl)imide.
  • compositions of the present disclosure can also have various lithium salts.
  • the lithium salts in the compositions of the present disclosure can include, without limitation, lithium hexafluorophosphate ("LiPFc” or “LiPF 6 "), lithium bis(trifluoromethylsulfonyl)imide (“LiTFSI”), lithium bis(fluorosulfonyl)imide (“LiFSI”), lithium bis(oxalato)borate (“LiBOB”), and combinations thereof.
  • the lithium salt is lithium bis(trifluoromethylsulfonyl)imide.
  • the compositions of the present disclosure include a mixture of hexagonal boron nitride, a piperidinium-based ionic liquid, and a lithium salt.
  • the compositions of the present disclosure can also be in various forms. For instance, in some embodiments, the compositions of the present disclosure are in the form of a composite material. In some embodiments, the compositions of the present disclosure have a consistency of a paste. In some embodiments, the compositions of the present disclosure are in the form of freestanding membranes, such as freestanding films.
  • compositions of the present disclosure also include a polymer binder.
  • the polymer binder maintains the compositions of the present disclosure in the form of a free standing membrane.
  • the polymer binder includes one or more thermoplastic polymers.
  • the thermoplastic polymers include, without limitation, poly(methyl methacrylate), polymethacrylic acid, polyvinylidene fluoride, acrylonitrile butadiene styrene, polylactic acid, polybenzimidazole, polycarbonate, polyether sulfone, poly ether ether ketone, polyetherimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyimide, polyacrylonitrile, polyurethane, and combinations thereof.
  • the polymer binder includes one or more thermosetting polymers.
  • the thermosetting polymers include, without limitation, polyimide, polyurethane, epoxy, polyester, and combinations thereof.
  • compositions of the present disclosure can have various advantageous properties.
  • the compositions of the present disclosure are thermally stable and nonvolatile.
  • the compositions of the present disclosure are operable and safe at high temperatures.
  • the compositions of the present disclosure have ionic conductivities that range from about 0.1 mS/cm to about 5 mS/cm. In some embodiments, the compositions of the present disclosure have ionic conductivities of about 3 mS/cm.
  • compositions of the present disclosure have electrochemical stability windows that range from about 1 V to about 6 V. In some embodiments, the compositions of the present disclosure have electrochemical stabilities of about 5 V at 120 °C.
  • the compositions of the present disclosure can demonstrate extended thermal stability. For instance, when used in combination with conventional electrodes, the compositions of the present disclosure can demonstrate thermal stability at temperatures above 100 °C for over 100 cycles with a total capacity fade of less than 5%. In some embodiments, the compositions of the present disclosure can demonstrate thermal and electrochemical stability for over 600 cycles at 120 °C, with a total capacity fade of less than 3%. In some embodiments, the compositions of the present disclosure can demonstrate thermal and electrochemical stability for over 50 cycles at 150 °C, with a total capacity fade of less than 2%.
  • the compositions of the present disclosure can demonstrate thermal and electrochemical stability for cycling periods of over 32 days. In some embodiments, the compositions of the present disclosure can demonstrate a self-discharge of less than 3% of capacity while stored at 120 °C for 24 hours in the fully charged state. In some embodiments, the compositions of the present disclosure can demonstrate thermal and electrochemical stability for storage times over 20 days at 120 °C. [0044] Methods of Making Compositions
  • the present disclosure pertains to methods of making the compositions of the present disclosure.
  • the methods of the present disclosure involve contacting a boron nitride, an ionic liquid and a lithium salt to form the composition.
  • the contacting of the different components of the compositions of the present disclosure can occur by various methods. For instance, in some embodiments, the contacting occurs by heating boron nitrides, ionic liquids, and lithium salts. In some embodiments, the contacting occurs by incubating boron nitrides, ionic liquids, and lithium salts. In some embodiments, the contacting occurs by mixing boron nitrides, ionic liquids, and lithium salts. In some embodiments, the mixing occurs by various methods, such as stirring, sonication, physical agitation, and combinations of such steps.
  • compositions of the present disclosure can be in various states during the contacting step.
  • the boron nitride is in solid form, and the ionic liquid and the lithium salt are in a solution.
  • compositions of the present disclosure can be in various ratios during the contacting step. For instance, in some embodiments where the boron nitride is in solid form and the ionic liquid and the lithium salt are in a solution, the contacting occurs at a 1:2 boron nitride to solution wt./wt. ratio. In some embodiments where the boron nitride is in solid form and the ionic liquid and the lithium salt are in a solution, the contacting occurs at a 1:2.5 boron nitride to solution wt./wt. ratio.
  • the contacting occurs at a 1:3 boron nitride to solution wt./wt. ratio. In some embodiments, equimolar ratios of boron nitrides, ionic liquids, and lithium salts are utilized during the contacting step.
  • the contacting of lithium salts and ionic liquids occurs in a solvent, such as an organic solvent. In some embodiments, the contacting results in the dissolution of the lithium salts with the ionic liquids in the solvent to form a solution. Thereafter, the boron nitride is combined with the formed solution by various methods described previously, such as by physical agitation.
  • the properties of the formed compositions may be tailored by adjusting the amounts of boron nitrides, ionic liquids and lithium salts that are mixed together.
  • the choice of the ionic liquids and the lithium salts can define the electrochemical properties of the formed composition while the choice of boron nitride can provide mechanical stability to the composition.
  • the methods of the present disclosure also include a step of incorporating the formed composition into an energy storage device.
  • the formed composition is utilized as an electrolyte, a separator, or an electrolyte- separator combination in the energy storage device.
  • the compositions of the present disclosure are formed by mixing a lithium salt with an ionic liquid (step 10). Thereafter, appropriate amounts of a boron nitride (e.g., hexagonal boron nitride) are mixed with the ionic liquid/lithium salt solution (step 12), thereby forming a composite (step 14). The formed composite is then incorporated into an energy storage device (step 16).
  • a boron nitride e.g., hexagonal boron nitride
  • the mixing of the ionic liquid/lithium salt solution with the boron nitride occurs by adding the boron nitride to the ionic liquid/lithium salt solution. In some embodiments, the mixing of the ionic liquid/lithium salt solution with the boron nitride occurs by adding the ionic liquid/lithium salt solution to the boron nitride.
  • the compositions of the present disclosure are formed by mixing lithium bis(trifluoromethylsulfonyl)imide ("LiTFSI”) with 1 -methyl- 1- propylpiperidinium bis(trifluoromethylsulfonyl)imide (a room temperature ionic liquid labeled as "RTIL”) to form a solution (step 20). Thereafter, appropriate amounts of a hexagonal boron nitride are mixed with the solution (step 22) to form a composition that resembles a conductive paste.
  • LiTFSI lithium bis(trifluoromethylsulfonyl)imide
  • RTIL room temperature ionic liquid labeled as
  • the present disclosure pertains to energy storage devices that contain the compositions of the present disclosure.
  • the energy storage devices include, without limitation, capacitors (e.g., electrochemical double-layer capacitors), super capacitors, micro supercapacitors, pseudo capacitors, batteries, photovoltaic devices, photovoltaic cells, and combinations thereof.
  • the energy storage devices of the present disclosure include a battery.
  • the battery includes, without limitation, micro batteries, lithium- ion batteries, lithium- sulfur batteries, sodium-ion batteries, magnesium-ion batteries, aluminum- ion batteries, and combinations thereof.
  • the battery is a lithium- ion battery.
  • compositions of the present disclosure may be utilized as various components of an energy storage device.
  • the compositions of the present disclosure are utilized as an electrolyte in the energy storage device.
  • the compositions of the present disclosure are utilized as a separator in the energy storage device.
  • the compositions of the present disclosure are utilized as an electrolyte and a separator in the energy storage device (i.e., an electrolyte-separator combination).
  • FIG. 1C An example of an energy storage device that contains a composition of the present disclosure is shown in FIG. 1C.
  • the energy storage device is lithium- ion battery 30.
  • Lithium-ion battery 30 contains anode 32, electrolyte component 34, and cathode 36.
  • Electrolyte component 34 in this example contains a composition of the present disclosure.
  • electrolyte component 34 can be an electrolyte composite, a separator, or an electrolyte- separator combination.
  • the present disclosure pertains to methods of making the energy storage devices of the present disclosure.
  • the methods include incorporating the compositions of the present disclosure as components of the energy storage device.
  • energy storage devices are fabricated by combining the compositions of the present disclosure with electrodes (e.g., combining electrolyte component 34 with anode 32 and cathode 36, as illustrated in FIG. 1C).
  • the energy storage devices of the present disclosure can have various advantageous properties. For instance, in some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures that range from about 20 °C to about 200 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures that range from about 20 °C to about 150 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures that range from about 20 °C to about 120 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures of more than about 80 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures of more than about 100 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures of more than about 120 °C. In some embodiments, the energy storage devices of the present disclosure are capable of being operated at temperatures of more than about 150 °C.
  • the energy storage devices of the present disclosure can also be operational at temperatures that are lower than the aforementioned operational temperatures. For instance, in some embodiments where an energy storage device is capable of being operated at temperatures of more than about 100 °C, the energy storage device can also be operational at temperatures that are below 100 °C. [0063] In some embodiments, the energy storage devices of the present disclosure have a theoretical capacity of more than about 100 mAh/g at 120 °C. In some embodiments, the energy storage devices of the present disclosure have a theoretical capacity of more than about 160 mAh/g at 120 °C. In some embodiments, the energy storage devices of the present disclosure have a theoretical capacity of more than about 175 mAh/g at 120 °C.
  • the energy storage devices of the present disclosure have a stable capacity retention over 100 cycles. For instance, in some embodiments, the energy storage devices of the present disclosure have a stable capacity retention over 600 cycles of recharging at high current rates of 3C. In some embodiments, the energy storage devices of the present disclosure have a stable capacity retention over 100 cycles of recharging at high current rates of 1C. In some embodiments, the energy storage devices of the present disclosure have a stable capacity retention over 100 cycles of recharging at current rates of C/3. In some embodiments, the energy storage devices of the present disclosure have a stable capacity retention over 100 cycles of recharging at current rates of C/8.
  • Example 1 Hexagonal Boron Nitride-Based Electrolyte Composite for Li-Ion Battery Operation from Room Temperature to 150 °C
  • a stoichiometric mixture of hexagonal boron nitride, piperidinium-based ionic liquid and a lithium salt has been formulated, with ionic conductivity reaching 3 mS/cm, electrochemical stability higher than 5 V vs Li/Li + and extended thermal stability.
  • the composite was used in combination with conventional electrodes and demonstrated to be stable for over 600 cycles at 120 °C, with a total capacity fade of less than 3%.
  • Electrolytes were prepared by mixing bentonite clay or hexagonal boron nitride ("h-BN”) with an appropriate weight of a 1 mol L “1 solution of lithium bis(trifluoromethylsulfonyl)imide (“LiTFSI”) in the ionic liquid 1 -methyl- 1 -prop ylpiperidinium bis(trifluorosulfonyl)imide (“PP13").
  • LiTFSI lithium bis(trifluoromethylsulfonyl)imide
  • PP13 -methyl-methyl-prop ylpiperidinium bis(trifluorosulfonyl)imide
  • bentonite and boron nitride have a similar flake size of ⁇ 1 ⁇
  • h-BN was found to absorb twice as much room temperature ionic liquid (“RTIL”) solution as clay before it reached the same paste-like consistence. Without being bound by theory, such observations are likely due to a higher specific volume of the h-BN powder.
  • the pre-exponential factor A is proportional to the number of charge carriers in the electrolyte. Although factor A evidently dropped with addition of ceramic components, Applicants note that the ratio between A h -BN and A c i ay is ⁇ 2. Assuming that both composites have comparable densities, this factor is larger than expected, likely due to the presence of -30% more ionic liquid solution in the h-BN system. The results suggest that the actual nature of ceramic within the electrolyte impacts the ion distribution and the effective free volume.
  • Applicants also observed that the presence of ceramic particles resulted in a decrease in the pseudo-activation energy, possibly due to a local partial screening of coulombic interactions in the ionic liquid, with a more significant effect observed with the presence of the charged platelets of clay.
  • the ideal glass transition temperature is higher in the composites than in the RTIL solution, indicating stronger solute- solvent interactions.
  • the lithium ion transference number (“ ⁇ + ”) was measured following an ac/dc polarization method (Evans et al., Polymer, 1987, 28, 2324). The technique is based on the assumption that, in a symmetric cell containing electrodes which are non-blocking only towards lithium ions, the application of a constant bias over a long time leads to a steady state, in which the overall current flow corresponds to the flux of lithium ions only.
  • a typical polarization measurement is shown in FIG. 7A, with the impedance plots before and after applying the bias shown as inset.
  • the resistance of the passivation layer formed on top of the lithium metal electrodes were in the range of hundreds of ohms at room temperature, quickly dropping upon heating the cell (FIG. 7B).
  • T Li+ at 23 °C was found to be 0.093+0.029, 0.076+0.009 and 0.060+ 0.001 for the 1 mol L "1 solution of LiTFSI in PP13, the h-BN composite, and the clay composite, respectively.
  • the values were in the same range of other reports for ionic liquids in the literature.
  • the negatively charged clay platelets may influence the ion mobility in the electrolyte.
  • Ceramic fillers at small concentrations have been widely reported to improve transport properties in polymer electrolytes by promoting salt dissociation and avoiding chain recrystallization. Nevertheless, at higher concentrations, the particles tend to aggregate, reducing the effective contact area with the electrolyte and negatively affecting charge transport.
  • the clay composite Since the clay composite has a high solid content, the actual role of the ceramic particles might be reduced due to phase segregation. Another factor to consider is that ion exchange might be happening at a small extent between the liquid phase and the clay, thus depleting the concentration of Li + in the electrolyte and reducing the transference number. Due to the improved ionic conductivity and lithium ion mobility, the h-BN-based composite was further characterized for use in LIBs operating at a wide temperature range.
  • the h-BN composite has a uniform distribution of boron nitride particles and ionic liquid, as observed using scanning electron microscopy in FIG. 8.
  • the specific interactions between the two phases are very weak and no major changes were observed in the Raman spectrum of the composite, as compared to the 1M solution of LiTFSI in ionic liquid (full data not shown here).
  • the solvation of lithium ions by TFSI " can be monitored by analyzing the band at -745 cm "1 assigned to the full anion vibration, as shown in FIG. 2C. This band can be resolved into two components, originated from the vibration of free anion (-742 cm “1 ) and Li + - bound TFSI " (748 cm "1 ).
  • addition of lithium salt increases the fraction of anions involved in strong solvation, as indicated by the enhanced intensity of the high frequency component.
  • the analysis of the spectra also show that addition of boron nitride increases the relative area of the bound TFSI " component by -5%, showing that Li+ is actually more intensely solvated by the anions in the presence of the ceramic.
  • the boron nitride-RTIL composite presented adequate conductivity and stable Li + transport properties in the range of 23 °C to at least 120 °C.
  • the successful application in LIBs requires compatibility with an appropriate potential range, without the presence of unwanted reactions.
  • FIG. 2D demonstrates that the anodic stability of the RTIL at high temperature increases after addition of LiTFSI, with an even larger enhancement attained when h-BN is mixed with the RTIL-based solution.
  • the electrochemical window was found to be broader than 4.7 V (from 5 V down to ⁇ 0.3 V vs Li/Li + ) at 120 °C, thus enabling its use with high energy density cathodes and anodes. Since the anodic stability might be strongly related to the reactivity of TFST, the intensification of Li-TFSI interactions with addition of h-BN, as observed by Raman spectroscopy, might explain the observation of a wider electrochemical window.
  • the electrolyte was also found to be compatible with lithium metal electrodes, showing a reversible plating/stripping behavior both at room and high temperatures (FIGS. 9B-C).
  • High energy density anode materials generally rely on the formation of a stable passivation layer to achieve stable performance. Moreover, it is rather unpredictable how the complex and heterogeneous structure of a passivation layer would behave if exposed to such conditions.
  • FIG. 3B shows the cyclic stability for a cell cycled at a -C/8 rate, where the capacity is nearly constant at 158 mAh g "1 for more than 50 cycles and a total test time of over a month.
  • the lithiation kinetics was found to be so favored at high temperatures that changing the C-rate had only minor effects on the delivered capacity (FIG. 10E).
  • the absence of thermal runway on the cells and the non-flammability and negligible vapor pressure of the electrolytes show that the h-BN composite allows reliable and safe operation for Li-ion batteries.
  • thermogravimetric analysis TGA
  • alkylimidazoles were being formed after heating certain imidazolium-based RTILs for 24 hours at temperatures above 120 °C.
  • FIG. 15A The profiles of the galvanostatic charge/discharge cycles before and after the self- discharge, along with the self-discharge curve itself, are shown in FIG. 15A.
  • the cell potential quickly rises to a value slightly lower than the plateau voltage for LTO.
  • the capacity retrieved from the cell after 24 hours of open circuit at 120 °C corresponds to 97% of the cell capacity.
  • no permanent capacity loss was observed after the self-discharge (FIG. 15B).
  • FIG. 4A shows a cyclic voltammetry at 150 °C for a LTO half-cell, showing that the electrochemical stability of the electrolyte holds up at higher temperatures and that the mechanical properties of the h-BN system is still large enough to avoid short-circuits.
  • the peaks display some extent of broadening after the first few cycles, the cell is able to deliver a stable capacity with a high coulombic efficiency of 97% (FIG. 4B).
  • a change in the shape of the peaks was also observed in CV measurements with slower scan rates and appeared to be time-dependent.
  • such patterns may be due to changes in the electrode that affect the overall kinetics of the device, possibly involving redistribution of the polyvinylidene fluoride ("PVDF”) binder.
  • PVDF polyvinylidene fluoride
  • Applicants present an electrolyte composite based on hexagonal boron nitride and ionic liquid that allows Li-ion battery operation with high efficiency over an unprecedented temperature range, spanning at least from 24 °C to 150 °C.
  • the presence of a ceramic component in the electrolyte had little overall effect on the transport properties, although contributing to an increase of the electrochemical window.
  • the composite was also shown to be compatible towards a cathode material, enabling full-cell testing at high temperatures.
  • Example 1.1 Electrode preparation, electrolyte composition and cell assembly
  • Electrodes were fabricated by coating slurries containing 80% active material, 10% graphite and 10% poly(vinilydene difluoride) binder onto current collectors.
  • the h-BN composite was prepared by mixing boron nitride powder and a 1 mol L "1 solution of LiTFSI in the RTIL 1 -methyl- 1 -prop ylpiperidinium bis(trifluorosulfonyl)imide, in a 1:2 wt./wt. ratio. More detailed protocols are provided herein.
  • the electrodes were prepared by grinding the active materials for the anode (Lithium Titanate, "LTO”, ⁇ 200 nm particle size, spinel, Sigma- Aldrich) or the cathode (extra-lithiated manganese oxide, Lii +x Mn 2 - x 0 4 , "LMO", synthesis described below) with ultra-fine graphite and poly(vinilydene difluoride) ("PVDF", Sigma- Aldrich), in a proportion of 80: 10: 10 and adding enough N-methyl-2- pyrrolidinone (“NMP", Sigma- Aldrich) to form a viscous slurry. The slurry was then cast onto copper current collectors (1.21 cm ), by either manually coating or spray coating.
  • anode Lithium Titanate, "LTO”, ⁇ 200 nm particle size, spinel, Sigma- Aldrich
  • the cathode extra-lithiated manganese oxide, Lii +x Mn 2 - x 0 4 , "
  • Electrodes were then dried for at least 24 hours at 85 °C under vacuum.
  • Typical loadings were in the range of 2-5 mg for anodes and 5-7 mg for cathodes, depending on the technique employed for casting the slurry.
  • Typical thicknesses are in the order of 30-40 ⁇ for both electrodes.
  • the electrolyte was prepared by thoroughly mixing appropriate amounts of bulk boron nitride powder ( ⁇ 1 pm flakes, Sigma- Aldrich) or bentonite clay ( ⁇ 1 pm flakes, Southern Clay Products) and a 1 mol L "1 solution of bis(trifluoromethylsulfonyl)imide lithium salt (“LiTFSI”) in the room temperature ionic liquid (“RTIL”) 1 -methyl- 1 -prop ylpiperidinium bis(trifluoromethylsulfonyl)imide (“PP13").
  • the concentration of the RTIL solution was selected based on ionic conductivity and Li-ion transference number measurements (FIGS. 7D-E).
  • the paste-like mixture had a 1:2 BN- and 1: 1 clay-to-solution ratio.
  • the typical total weight of the electrolyte was -150 mg per cell.
  • the paste was manually cast onto the electrode until the whole area was covered, forming a layer with typically 250-300 ⁇ of thickness.
  • Both coin cells and Swagelok-type cells were tested and provided similar results.
  • Electrolyte preparation and cell assembly were performed in an Argon-filled glovebox with moisture and oxygen levels inferior to 0.1 ppm.
  • Several results for cells operating at high temperature were compared to conventional cells tested at room temperature for validation, in which a 1 mol L "1 solution of LiPF6 in 1: 1 v/v ethylene carbonate/dimethyl carbonate was used as electrolyte.
  • Example 1.2 Electrochemical characterization
  • CD Galvanostatic Charge-Discharge
  • CV Cyclic Voltammetry
  • EIS Electrochemical Impedance Spectroscopy
  • Example 1.3 Cathode active material synthesis
  • Example 1.4 Ionic conductivity modeling
  • Equation 1 The experimental data was fitted using the following Vogel-Tammann-Fuchel equation (Equation 1). [00119] In Equation 1, o is the ionic conductivity, A is a pre-exponential factor, T is the absolute temperature, T 0 is the ideal glass transition temperature, and E a is a pseudo-activation energy. VTF plots for all samples are shown in FIG. 6 and the fitted parameters are listed in Table 1.
  • Lithium ion transference numbers were calculated using the equation as modified by Choe et al. (Chem. Mater., Vol. 9, pp. 369-379, 1997), accounting for variations in the electrolyte resistance (Equation 2).
  • Ri and R f are the bulk resistances before and after the dc polarization, respectively.
  • R p is the resistance of the passivation layer on top of lithium metal.
  • I 0 is the initial current after applying the bias.
  • I s is the current in the steady state.
  • the bias applied to the cell to determine the lithium ion transference number should be small enough to keep a low concentration gradient within the electrolyte.
  • potentials in the order of 5 mV are commonly employed for the task.
  • the application of small biases leads to a large ohmic drop through the interface, and the effective potential in the electrolyte is too small to result in consistent readings.
  • the dc relaxation step required higher voltages (20-130 mV) only for measurements performed at room temperature. In all other cases, the actual iR drop in the electrolyte was typically kept in the range of 2-5 mV, low enough to comply with the low concentration gradient requirement.
  • the impedance spectra for some cells (-50% of 1M PP13 and -10% of h- BN composite) presented features that were not observed at other temperatures, as shown in FIG. 7C. The existence of two semicircles in the spectra can be ascribed to either a charge transfer resistance or to another passivation film. Resistances arising from both processes are expected to decrease with an increase in temperature, but the additional semicircle always seemed to present larger Rp values than it would be expected.
  • Example 1.5 Electrolyte characterization
  • Example 1.6 Room temperature performance of LTQ half-cells using the h-BN-RTIL composite electrolyte
  • Example 1.7 Electrode aging at high temperature
  • Example 1.8 Impedance evolution during cycling at 120 °C
  • Electrolyte aging effects seemed to be dominant at early stages, with larger resistances from the electrode aging taking over upon further cycling. On these same plots, it is possible to observe that the electrolyte resistance is nearly constant, even after extensive cycling, further indicating the stability of the composite.
  • Example 1.9. Self-discharge tests The cells were initially cycled at 120 °C at a C/8 rate for 3 cycles, as shown in the blue curve in the profiles of FIG. 15A. Thereafter, the LTO was lithiated (charged) at a C/8 rate and then allowed to self-discharge (SD) (still at 120 °C, for 24 hours). The SD curve was recorded in an Autolab potentiostat and is shown in the red portion of FIG. 15A. It is possible to see that the potential quickly rises to a value close to the plateau potential until it stabilizes. After the time was over, the LTO was galvanostatically delithiated (C/8 rate) to evaluate the remaining charge stored in the cell. The half-cell was then cycled for two more cycles at the same rate to investigate if there was any irreversible loss of capacity.

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Abstract

Selon certains modes de réalisation, la présente invention concerne des compositions qui comprennent un nitrure de bore, un liquide ionique et un sel de lithium. De telles compositions peuvent être sous la forme d'un composite et utilisées comme un électrolyte, un séparateur, ou une combinaison électrolyte-séparateur dans un dispositif de stockage d'énergie. Selon d'autres modes de réalisation, la présente invention concerne des procédés de préparation des compositions de la présente invention par la mise en contact d'un nitrure de bore, d'un liquide ionique et d'un sel de lithium. Dans certains modes de réalisation, les procédés de la présente invention comprennent également une étape consistant à incorporer les compositions de la présente invention dans un dispositif de stockage d'énergie. Dans certains modes de réalisation, la présente invention concerne des dispositifs de stockage d'énergie qui contiennent les compositions de la présente invention. Dans certains modes de réalisation, le dispositif de stockage d'énergie est une batterie. Dans certains modes de réalisation, le dispositif de stockage d'énergie peut fonctionner à des températures supérieures à 100 °C.
PCT/US2016/020916 2015-03-04 2016-03-04 Composites nitrure de bore-liquide ionique et leur utilisation pour des dispositifs de stockage d'énergie WO2016141301A1 (fr)

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US20180159180A1 (en) * 2016-12-01 2018-06-07 The Regents Of The University Of California High temperature li-ion battery cells utilizing boron nitride aerogels and boron nitride nanotubes
WO2018153450A1 (fr) * 2017-02-22 2018-08-30 Toyota Motor Europe Processus de vieillissement à haute température de batterie au lithium-ion
WO2018185257A1 (fr) * 2017-04-05 2018-10-11 The Provost, Fellows, Scholars And Other Members Of Board Of Trinity College Dublin Dispositif multicouche et son procédé de fabrication
CN110994017A (zh) * 2020-01-03 2020-04-10 南京工业大学 一种氮化物增强的聚合物电解质、制备方法及长寿命固态锂离子电池
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CN115181305A (zh) * 2022-07-25 2022-10-14 河北金力新能源科技股份有限公司 改性聚酰亚胺质子交换膜及其制备方法
US11581572B2 (en) * 2018-10-09 2023-02-14 University Of Maryland, College Park Lithium metal nitrides as lithium super-ionic conductors
CN116178618A (zh) * 2023-03-14 2023-05-30 杭州蓝碳新材料有限公司 一种高导热聚离子液体/氮化硼复合绝缘材料及其制备方法

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US20180159180A1 (en) * 2016-12-01 2018-06-07 The Regents Of The University Of California High temperature li-ion battery cells utilizing boron nitride aerogels and boron nitride nanotubes
US11223071B2 (en) * 2016-12-01 2022-01-11 The Regents Of The University Of California High temperature Li-ion battery cells utilizing boron nitride aerogels and boron nitride nanotubes
WO2018153450A1 (fr) * 2017-02-22 2018-08-30 Toyota Motor Europe Processus de vieillissement à haute température de batterie au lithium-ion
US11024898B2 (en) 2017-02-22 2021-06-01 Toyota Motor Europe Lithium-ion battery high temperature aging process
WO2018185257A1 (fr) * 2017-04-05 2018-10-11 The Provost, Fellows, Scholars And Other Members Of Board Of Trinity College Dublin Dispositif multicouche et son procédé de fabrication
US11581572B2 (en) * 2018-10-09 2023-02-14 University Of Maryland, College Park Lithium metal nitrides as lithium super-ionic conductors
CN110994017A (zh) * 2020-01-03 2020-04-10 南京工业大学 一种氮化物增强的聚合物电解质、制备方法及长寿命固态锂离子电池
CN111193064A (zh) * 2020-01-09 2020-05-22 北京理工大学 一种固态聚合物离子凝胶电解质膜及其制备方法与应用
CN115181305A (zh) * 2022-07-25 2022-10-14 河北金力新能源科技股份有限公司 改性聚酰亚胺质子交换膜及其制备方法
CN115181305B (zh) * 2022-07-25 2023-11-03 河北金力新能源科技股份有限公司 改性聚酰亚胺质子交换膜及其制备方法
CN116178618A (zh) * 2023-03-14 2023-05-30 杭州蓝碳新材料有限公司 一种高导热聚离子液体/氮化硼复合绝缘材料及其制备方法
CN116178618B (zh) * 2023-03-14 2023-10-24 杭州蓝碳新材料有限公司 一种高导热聚离子液体/氮化硼复合绝缘材料及其制备方法

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